US4237301A - Two stage process for preparing 2,6-pyridin-dicarboxylic acid - Google Patents

Two stage process for preparing 2,6-pyridin-dicarboxylic acid Download PDF

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US4237301A
US4237301A US05/965,037 US96503778A US4237301A US 4237301 A US4237301 A US 4237301A US 96503778 A US96503778 A US 96503778A US 4237301 A US4237301 A US 4237301A
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stage
acid
addition compound
hours
pyridine
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Giovanni Ghelli
Enrico Bruschi
Gino Agnese
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Luigi Stoppani SpA
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Luigi Stoppani SpA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/803—Processes of preparation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • This invention relates to a two stage process for preparing 2,6-pyridin-dicarboxylic acid or dipicolinic acid from 2,6-dimethyl-pyridine through oxidation of the latter in an acidic environment with hexavalent chromium salts and formation of a molar addition compound between dicarboxylic acid, being formed by oxidation, ahd chromic anhydride in the first stage, and subsequent hot hydrolysis of the addition product so obtained, thus isolating 2,6-pyridin-dicarboxylic acid therefrom in the second stage.
  • the invention also comprises the above mentioned intermediate complex addition compound.
  • the invention also relates to 2,6-pyridin-dicarboxylic acid of high purity, obtained by the process according to the present invention.
  • the processes of the first group all provide a total yield between 45 and 50%, and require a sequence of purifying operations, in any case leading to a dipicolinic acid, which may be still contaminated with mono-potassium salt and potassium chloride. Moreover, due to long reaction times (17-24 hours) and peculiar characteristics of the processes, they have a maximum value of 2 in the ratio (in kg/cu.m. hour): ##EQU1## which ratio represents a specific potential production and is of significance when designing an industrial production plant.
  • the product (dipicolinic acid) being obtained is per se of a high commercial interest, particularly for its high purity, as well as for its properties of dicarboxylic and heterocyclic organic acid capable of forming esters, amides and various other derivatives, therefore being very suitable for use as raw material for organic syntheses of different kinds, even very specialized.
  • a monomer in the synthesis of polyester or polyamide type of copolymers a stabilizing agent for peroxides and peracids, for example t-butyl peroxide, dimethyl-cyclohexanon peroxide, peroxyacetic acid and peroxy-monosulphuric acid; ingredient for polishing solution of metal surfaces; stabilizing agent for organic materials susceptible to be deteriorated due to the presence of traces of metal ions (sequestrating effect); stabilizing agent for epoxy resins; stabilizing agent for photographic solutions or emulsions (preventing the precipitation of calcium salts).
  • a stabilizing agent for peroxides and peracids for example t-butyl peroxide, dimethyl-cyclohexanon peroxide, peroxyacetic acid and peroxy-monosulphuric acid
  • ingredient for polishing solution of metal surfaces stabilizing agent for organic materials susceptible to be deteriorated due to the presence of traces of metal ions (sequestrating effect); stabilizing agent for epoxy resin
  • the oxidizer for hexavalent chromium is sodium bichromate
  • the acidificant agent is sulphuric acid
  • the compound to be oxidized is 2,6-dimethyl-pyridine.
  • x, y, m and n respectively represent:
  • index x varies between 0.25 and 2.50, values representing an excess of 10 and 100%, respectively, the preferred variation field or range being between 0.5 and 1.0, corresponding to an excess of 20 and 50%, respectively.
  • y the moles of free acid per mole of complexed dipicolinic acid from CrO 3 formed; y varies between 3 and 20, preferably between 6 and 10;
  • m represents the water moles at the beginning of the reaction; as it will be better explained in the following, this index varies in accordance with the ranges or concentration selected for the reactants between 30 and 250, preferably between 40 and 150;
  • n represents the water moles in the hydrolysis reaction (of the second stage) for one mole of the addition compound formed by dipicolinic acid CrO 3 .
  • the weight ratio selected between complex salt and water in the range of 75-225, preferably between 135 and 165.
  • oxidation of methyl groups of 2,6-dimethyl-pyridine is carried out in an acidic environment, under particular conditions later specified, with hexavalent chromium salts, soluble in water, such as alkaline bichromates (sodium, potassium, lithium, preferably sodium), or also with chromic anhydride, using sulphuric acid as an acidifying agent.
  • hexavalent chromium salts such as alkaline bichromates (sodium, potassium, lithium, preferably sodium), or also with chromic anhydride, using sulphuric acid as an acidifying agent.
  • the process is carried out with excess proportions of the oxidizer in solution with respect to the equivalent stoichiometrical value required by lutidine, as such conditions are the optimum conditions for the formation and isolation of the addition compound between dipicolinic acid and CrO 3 , formation of which is essential and characterizing for the isolation of dipicolinic acid.
  • This addition product is a novel product and it is intended to be claimed in the present invention.
  • the process which may be carried out as a batch process or semi-continuous and even continuous process, enables total yields, calculated on the theoretical value obtainable in connection with 2,6-dimethyl-pyridine used, of higher than 80%, and up to 90%, where a continuous process is used.
  • FIGURE is a flow chart which illustrates an embodiment of the process in accordance with the present invention.
  • the reaction occurring in homogeneous phase is carried out between a solution of 2,6-dimethyl-pyridine in sulphuric acid, having a concentration of 50-80% by weight (preferably between 60 and 70%), and a solution of sodium bichromate having a concentration (expressed as CrO 3 ) of 40-65% by weight (preferably 45-50% by weight).
  • bichromate is in excess relative to the stoichiometric amount required by lutidine for the formation of the addition compound mole/mole of dipicolinic acid with chromic anhydride.
  • Such an excess is the range of 10-100% (preferably 20-50%).
  • the operation is carried out by gradually introducing the two reactants, organic (of lutidine sulphuric solution) and inorganic (bichromate solution) into a vessel of anticorrosive material (preferably enameled) under stirring and already containing the so-called "initial reaction foot", comprising 20-50% (preferably 35-45%) total sulphuric acid at the designed concentration and 10-40% (preferably 15-25%) total filtrate as recycled from filtering of the final reaction mass of a previous operation.
  • reaction foot This "moderating" function of the "reaction foot" is not required in a continuous type of process, as being provided by the mass in the reactor during all of the reactant introducing steps.
  • the reaction in A is carried out at a temperature of 70°-115° C. (preferably 80°-110° C.) and takes a total time of 2-3 hours (initial period) for the introduction of the reactants, plus 3-0.5 hours (preferably 2-1 hours) for the actual reaction (time varying in accordance with temperature). Thus, a complete conversion of lutidine is obtained.
  • the mass obtained is cooled down to room temperature and the mass is filtered, thereby obtaining the separation of a liquid comprising a solution (aqueous solution) of chromium and sodium sulphate, also having therein the excess (relative to stoichiometrical) of introduced sulphuric acid and bichromate, and an orange-red crystalline solid which is washed and dried and has the following percent analytic compositon:
  • the addition compound is supplied to the second stage, where it is treated with water at a ratio of water and solid (considered as dried) in the range of 5 and 15 (preferably in the range of 9 and 11), at 100°-50° C. (preferably at 100°-80° C.) for 0.5-4 hours (preferably 1-2 hours).
  • room temperature preferably the range of 0°-15° C.
  • crystallized dipicolinic acid is obtained without crystallization water, which is then filtered, washed, and dried.
  • the product so obtained has a titer of 99.5% ⁇ 0.2, m.p. 253° ⁇ 1° C. and has the following analytic data:
  • the filtrate of dipicolinic acid is partly recycled to the hydrolysis reaction, partly to the preparing of diluted sulphuric acid which is for the reaction of the first stage, and partly is supplied to the liquid effluent for the recovery of chromium salts.
  • a universal type of laboratory reactor equipped with a stirrer was charged with 400 g 65% sulphuric acid by weight, with 370 g aqueous solution comprising 80 g chromium sulphate, 40 g sodium sulphate, 130 g 65% sulphuric acid by weight, 20 g chromic anhydride and 100 g water.
  • the temperature was set to about 100° C. and, following introduction of the reactants, the reaction was continued for one hour at the same temperature.
  • the mixture was cooled by stirring to about 25° C. and filtered, obtaining after washing with water an orange-red crystalline solid (dry weight 96 g) which was dispersed in 1200 g water and heated at 100° C. for one hour.
  • the product was cooled to about 20° C., filtered, washed and dried, obtaining 65 g crystalline white product which by analysis was 2,6-pyridin-dicarboxylic acid (titer 99.7%).
  • Example 1 The reactor described in Example 1 was charged with 420 g liquid filtered from the reaction mass of Example 1 and 560 g 65% sulphuric acid.
  • This solid was dispersed in 800 g water, heated for one hour at 90° C. and, after cooling, filtering and washing, 48 g 2,6-pyridin-dicarboxylic acid (titer 99.8%) were obtained.
  • the reactor described in the preceding examples was charged with 370 g liquid filtered from the reaction masses of the preceding examples and 400 g 65% sulphuric acid by weight.
  • a universal type of pilot reactor was charged with 10.0 kg 65% sulphuric acid by weight, and 9.3 kg of a mixture of filtrates from the same type of preceding reactions carried out on laboratory scale.
  • inorganic reactant 17.38 kg aqueous solution of sodium bichromate, prepared to contain 8.17 kg chromic anhydride.
  • the reaction was continued still under stirring for one further hour at about 115° C.
  • 2.5 liters water were evaporated.
  • the product was cooled down to room temperature, the reacted mass was filtered, the solid was washed with 2 liters water and an orange-red crystalline product was obtained, weighing 2.96 kg (corresponding to 2.82 kg dried), and 33.5 liters filtrate (52.81 kg by weight).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
US05/965,037 1977-12-01 1978-11-30 Two stage process for preparing 2,6-pyridin-dicarboxylic acid Expired - Lifetime US4237301A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
IT30273/77A IT1089429B (it) 1977-12-01 1977-12-01 Procedimento in due stadi per preparare acido 2-6-piridin-bicarbossilico

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US06167222 Continuation 1980-07-09

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Country Status (12)

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US (1) US4237301A (fr)
JP (1) JPS5490181A (fr)
AT (1) AT366668B (fr)
BE (1) BE872394A (fr)
CA (1) CA1108617A (fr)
CH (1) CH640226A5 (fr)
DE (2) DE2857637C2 (fr)
ES (1) ES475546A1 (fr)
FR (1) FR2410650A1 (fr)
GB (1) GB2009163B (fr)
IL (1) IL56090A0 (fr)
IT (1) IT1089429B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4419515A (en) * 1977-12-01 1983-12-06 Luigi Stoppani S.P.A. Two stage process for preparing 2,6-pyridinedicarboxylic acid
US4857231A (en) * 1988-06-06 1989-08-15 Iowa State University Research Foundation, Inc. Thermochromic platinum complexes

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ291059B6 (cs) * 1997-03-12 2002-12-11 Lonza Ag Způsob výroby esterů 2,6-pyridindikarboxylových kyselin

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2415147A (en) * 1942-08-27 1947-02-04 Allied Chem & Dye Corp Process for oxidation of heterocyclic nitrogen compounds
FR976594A (fr) 1942-04-30 1951-03-20 Ig Farbenindustrie Ag Procédé de fabrication de pyridine
US2578672A (en) * 1945-11-23 1951-12-18 Koppers Co Inc Picolinic acid recovery
US3154549A (en) * 1961-10-23 1964-10-27 Wyandotte Chemicals Corp Process for the preparation of carboxylic acids
US3313821A (en) * 1964-08-03 1967-04-11 Chemlek Laboratotries Inc Process for preparing pyridine carboxylic acids from compounds having a pyridine nucleus
US3334021A (en) * 1964-04-09 1967-08-01 Monsanto Co Process for preparing dipicolinic acid
DE1620174C (de) 1972-11-16 Rütgerswerke AG, 6000 Frankfurt Verfahren zur oxydativen Herstellung von Pyridin^.o-dicarbonsäure
DE2300056A1 (de) 1973-01-02 1974-07-04 Kali Chemie Pharma Gmbh Verfahren zur gewinnung von pyridin2,6-dicarbonsaeure auf fermentativem wege

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE741321C (de) * 1941-02-13 1943-11-09 Ig Farbenindustrie Ag Verfahren zur Herstellung von Pyridin bzw. Pyridincarbonsaeuren
SU568642A1 (ru) * 1975-07-11 1977-08-15 Ордена Трудового Красного Знамени Институт Органического Синтеза Ан Латвийской Сср Способ получени пиридинкарбоновых кислот
IT1077343B (it) * 1977-07-18 1985-05-04 Stoppani Luigi Di Stoppani P & Procedimento di ossidazione altamente selettivo per preparare acidi piridincarbossilici

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1620174C (de) 1972-11-16 Rütgerswerke AG, 6000 Frankfurt Verfahren zur oxydativen Herstellung von Pyridin^.o-dicarbonsäure
FR976594A (fr) 1942-04-30 1951-03-20 Ig Farbenindustrie Ag Procédé de fabrication de pyridine
US2415147A (en) * 1942-08-27 1947-02-04 Allied Chem & Dye Corp Process for oxidation of heterocyclic nitrogen compounds
US2578672A (en) * 1945-11-23 1951-12-18 Koppers Co Inc Picolinic acid recovery
US3154549A (en) * 1961-10-23 1964-10-27 Wyandotte Chemicals Corp Process for the preparation of carboxylic acids
US3334021A (en) * 1964-04-09 1967-08-01 Monsanto Co Process for preparing dipicolinic acid
US3313821A (en) * 1964-08-03 1967-04-11 Chemlek Laboratotries Inc Process for preparing pyridine carboxylic acids from compounds having a pyridine nucleus
DE2300056A1 (de) 1973-01-02 1974-07-04 Kali Chemie Pharma Gmbh Verfahren zur gewinnung von pyridin2,6-dicarbonsaeure auf fermentativem wege

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
Black et al., Journ. Org. Chem., 14 (1949), p. 14. *
Epstein, Liebig's Ann. d. Chem., 231, (1895), pp. 24-36. *
Henge, Ber., 67, B (1934), pp. 750-753. *
Hodson et al., J. Bacteriol., 91(2), (1966), pp. 562-569. *
Ladenburg, Liebig's Ann. d. Chem., 247, (1888), pp. 32-41. *
Soine et al., Journal Ann. Pharm. Ass., 39, (1950), p. 421. *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4419515A (en) * 1977-12-01 1983-12-06 Luigi Stoppani S.P.A. Two stage process for preparing 2,6-pyridinedicarboxylic acid
US4857231A (en) * 1988-06-06 1989-08-15 Iowa State University Research Foundation, Inc. Thermochromic platinum complexes

Also Published As

Publication number Publication date
FR2410650A1 (fr) 1979-06-29
IL56090A0 (en) 1979-01-31
ES475546A1 (es) 1979-04-01
ATA834378A (de) 1981-09-15
JPS6121470B2 (fr) 1986-05-27
DE2813417C3 (de) 1986-07-10
AT366668B (de) 1982-04-26
JPS5490181A (en) 1979-07-17
GB2009163B (en) 1982-06-30
FR2410650B1 (fr) 1983-02-11
CA1108617A (fr) 1981-09-08
GB2009163A (en) 1979-06-13
IT1089429B (it) 1985-06-18
CH640226A5 (it) 1983-12-30
DE2813417A1 (de) 1979-06-07
DE2813417B2 (de) 1981-02-19
BE872394A (fr) 1979-03-16
DE2857637C2 (de) 1986-10-30

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